Internal olefin sulfonate composition

ABSTRACT

Provided are an internal olefin sulfonate composition which is capable of sufficiently enhancing foamability, light foam quality, and instantaneous foam dissipation property, and a cleansing composition containing the internal olefin sulfonate composition. The internal olefin sulfonate composition comprises (A) an internal olefin sulfonate having 12 carbon atoms and (B) an internal olefin sulfonate having 14 carbon atoms, wherein a content mass ratio of the component (A) to the component (B), (A/B), is from 10/90 to 90/10, and a total content of the component (A) and the component (B) in the internal olefin sulfonate is from 60 to 100% by mass.

This application is a Continuation of U.S. patent application Ser. No.14/766,059 filed on Aug. 5, 2015, which is the National Phase ofPCT/JP2014/052258 filed Jan. 31, 2014, which claims priority under 35U.S.C. §119(a) to Patent Application No. 2013-025319 filed in Japan onFeb. 13, 2013, all of which are hereby expressly incorporated byreference into the present application.

FIELD OF THE INVENTION

The present invention relates to an internal olefin sulfonatecomposition useful as a base for a cleansing agent, and to a cleansingcomposition containing the internal olefin sulfonate.

BACKGROUND OF THE INVENTION

Anionic surfactant, particularly, alkyl sulfate and alkylpolyoxyalkylene sulfate, is excellent in detergency and foaming power,and thus are widely used as cleansing ingredients for domestic orindustrial use. An olefin sulfonate, particularly, an internal olefinsulfonate obtained with an internal olefin having a double bond insidean olefin chain, not at its end, as a raw material, has been reported asone of anionic surfactants.

Such an internal olefin sulfonate is generally obtained by sulfonatingan internal olefin through reactions with a gaseous sulfurtrioxide-containing gas, followed by neutralization and then hydrolysisof the resulting sulfonic acid. For example, Patent Documents 1 to 3disclose improved production methods thereof.

The internal olefin sulfonate thus obtained is known to have goodbiodegradability or the like, but is still insufficient in a basicperformance as a cleansing agent including foamability and foam quality,compared with general-purpose surfactants such as alkyl polyoxyalkylenesulfuric acid ester salt. Thus, further improvement in such a basicperformance has been desired. As more people have concerned thewater-saving or consumers' preferences have been diversified in recentyears, the additional value of light foam quality and instantaneous foamdissipation property in addition to good foamability has also beenrequired for use as a major activator in laundry detergents, dishwashingdetergents, shampoos or the like. Specifically, it has been desired todevelop a surfactant composition which allows foam to spread quickly bybringing about light foam quality derived from large bubbles and lowbubble density and low foam viscosity during cleansing and alsofacilitates pleasant cleansing and rinsing in a short time by havinginstantaneous foam dissipation property quickly during rinsing. Such anadditional value is useful for, for example, hair shampoos and bodycleansers. As more people have a habit to wash their hair or bodieswithin a limited time before leaving the house after awakening or beforegoing to bed, it tends to spend a considerable amount of time forspreading foam throughout their hair or thoroughly rinsing their hair.This is largely due to fine foam quality and high foam viscosity. If asurfactant composition having light foam quality and instantaneous foamdissipation property can be formulated in a shampoo, the resultingshampoo permits sufficient cleansing in a short time, and not onlyachieves pleasant cleansing but can bring about a refreshed feel afterdrying, leading to the realization of water-saving.

Patent Document 4 discloses a specific internal olefin sulfonic acidwhich is intended to impart the solubilizing ability, penetratingability, and interfacial tension reducing ability as a cleansingcomponent. It discloses that when it is used, for example, as a shampoo,it lathers well, and achieves an improved feel without friction. PatentDocument 5 also describes a specific internal olefin sulfonate for thepurpose of improving detergency, and discloses examples of applicationto shampoos, liquid soaps, and the like. Meanwhile, Patent Document 6describes a promoter for recoverying an oil using a surfactantcontaining a plurality of internal olefin sulfonates differing in thenumber of carbon atoms.

[Patent Document 1] JP-A-01-272564

[Patent Document 2] JP-A-61-134366

[Patent Document 3] JP-A-60-32759

[Patent Document 4] JP-A-2003-81935

[Patent Document 5] U.S. Pat. No. 5,078,916

[Patent Document 6] WO-A 2010/129051

SUMMARY OF THE INVENTION

The present invention relates to an internal olefin sulfonatecomposition comprising (A) an internal olefin sulfonate having 12 carbonatoms and (B) an internal olefin sulfonate having 14 carbon atoms,wherein a content mass ratio of the component (A) to the component (B),(A/B), is from 10/90 to 90/10, and a total content of the component (A)and the component (B) is from 60 to 100% by mass.

DETAILED DESCRIPTION OF THE INVENTION

Further improvement is still required for any of the compositionsdescribed in the above-mentioned documents to exert good foamabilitytogether with light foam quality and instantaneous foam dissipationproperty at high levels as a cleansing agent which is applied to hair,skin, or the like.

Therefore, the present invention relates to an internal olefin sulfonatecomposition which is capable of sufficiently enhancing good foamability,light foam quality, and instantaneous foam dissipation property, and acleansing composition containing the internal olefin sulfonate.

The present inventors studied a length of an aliphatic chain in aninternal olefin sulfonate, a ratio thereof and other various conditions,and consequently found that an internal olefin sulfonate compositionwhich has good foamability together with light foam quality andinstantaneous foam dissipation property can be obtained by setting theratio between an internal olefin sulfonate having 12 carbon atoms and aninternal olefin sulfonate having 14 carbon atoms to a predeterminedrange while setting the total content thereof to a predetermined range.On the basis of these findings, the present invention has beencompleted.

According to the present invention, it can provide an internal olefinsulfonate composition which satisfies good foamability, also bringsabout light foam quality derived from large bubbles and low bubbledensity and foam viscosity which allow foam to spread quickly duringcleansing, also permits pleasant cleansing by bringing aboutinstantaneous foam dissipation property capable of dissipating foam atonce during rinsing, and can further adequately bring about a good feelwithout perceivable residues from the cleansing agent after cleansingand subsequent towel drying, for example, and a cleansing compositioncontaining the internal olefin sulfonate.

Hereinbelow, the present invention will be described in detail.

<Internal Olefin Sulfonate Composition>

The internal olefin sulfonate composition of the present inventionincludes (A) an internal olefin sulfonate having 12 carbon atoms and (B)an internal olefin sulfonate having 14 carbon atoms, in which a contentmass ratio of the component (A) to the component (B), (A/B), is from10/90 to 90/10, and a total content of the component (A) and thecomponent (B) is from 60 to 100% by mass.

In the present invention, an internal olefin sulfonate is a sulfonateobtained by sulfonating an internal olefin (an olefin having a doublebond inside the olefin chain) as the raw material, followed byneutralization and then hydrolysis, as described above. That is,sulfonation of an internal olefin quantitatively produces β-sultone,some of which are converted into γ-sultone and olefin sulfonic acid,which are further converted into hydroxyalkane sulfonate and olefinsulfonate in the process of neutralization and hydrolysis (for example,J. Am. Oil Chem. Soc. 69, 39 (1992)). It should be noted that the aboveinternal olefin may also has a broad meaning including a trace amount ofso-called α-olefin, in which a double bond is present at the C-1position of the carbon chain. Here, the hydroxyl group of thehydroxyalkane sulfonate thus obtained is present inside the alkanechain, and the double bond of the olefin sulfonate thus obtained ispresent inside the olefin chain. The product thus obtained is mainly amixture of the aforementioned substances, some of which may include atrace amount of hydroxyalkane sulfonate having a hydroxyl group at theend of the carbon chain, or olefin sulfonate having a double bond at theend of the carbon chain. In the present specification, each of theseproducts and a mixture thereof are collectively referred to as aninternal olefin sulfonate. Hydroxyalkane sulfonate is referred to as ahydroxy form of an internal olefin sulfonate (hereinbelow, may also bereferred to as HAS), and olefin sulfonate is referred to as an olefinform of an internal olefin sulfonate (hereinbelow, may also be referredto as IOS).

A content mass ratio of the component (A) to the component (B), (A/B),in the internal olefin sulfonate composition of the present invention isfrom 10/90 to 90/10 and is preferably from 25/75 to 90/10, morepreferably from 50/50 to 90/10, more preferably from 75/25 to 90/10, andeven more preferably from 80/20 to 90/10, from the viewpoint of lightfoam quality, instantaneous foam dissipation property, and a feel afterdrying. The content mass ratio of the component (A) to the component(B), (A/B), in the internal olefin sulfonate composition of the presentinvention is preferably from 10/90 to 80/20, more preferably from 10/90to 70/30, more preferably from 10/90 to 30/70, and even more preferablyfrom 10/90 to 20/80, from the viewpoint of foamability.

The content mass ratio of the component (A) to the component (B), (A/B),in the internal olefin sulfonate composition is a numerical valuemeasured by a high-performance liquid chromatograph-mass spectrometer(hereinbelow, abbreviated as HPLC-MS). Specifically, an internal olefinsulfonate having 12 carbon atoms and an internal olefin sulfonate having14 carbon atoms are separated by HPLC, each of which then is identifiedby analysis with MS. From the HPLC-MS peak area thereof, the contentmass ratio of the component (A) to the component (B), (A/B), in theinternal olefin sulfonate composition is determined.

The total content of the component (A) and the component (B) in theinternal olefin sulfonate composition of the present invention is from60 to 100% by mass. The lower limit of the total content of thecomponent (A) and the component (B) is preferably 70% by mass or more,more preferably 80% by mass or more, more preferably 90% by mass ormore, more preferably 95% by mass or more, more preferably 96.5% by massor more, and even more preferably 97% by mass or more, from theviewpoint of foamability, light foam quality, instantaneous foamdissipation property, and a feel after drying.

As is apparent from the aforementioned production method, the sulfonategroup in the internal olefin sulfonate of the present invention ispresent inside the olefin chain or alkane chain. In the presentinvention, it is preferable that the content of an internal olefinsulfonate in which the sulfonate group is present at the C-2 position ofthe olefin chain or alkane chain is low, while the content of aninternal olefin sulfonate in which the sulfonate group is presentfurther inside is high, from the viewpoint of foamability, light foamquality, instantaneous foam dissipation property, and a feel afterdrying. It is more preferable that the content of an internal olefinsulfonate in which the sulfonate group is present at the C-2 position ofthe olefin chain or alkane chain is low, with respect to both of theabove internal olefin sulfonate having 12 carbon atoms and 14 carbonatoms.

A content of the internal olefin sulfonate in which a sulfonate group ispresent at a C-2 position in the internal olefin sulfonate (component(A) and component (B)) having 12 and 14 carbon atoms of the presentinvention is, in the total content of the component (A) and thecomponent (B), preferably 28% by mass or less, more preferably less than25% by mass, more preferably 23% by mass or less, and even morepreferably 22% by mass or less, from the viewpoint of light foam qualityand instantaneous foam dissipation property. The content of the internalolefin sulfonate in which a sulfonate group is present at a C-2 positionin the component (A) and the component (B) is, in the total content ofthe component (A) and the component (B), preferably 5% by mass or more,more preferably 7% by mass or more, more preferably 15% by mass or more,and even more preferably 19% by mass or more, from the viewpoint of costand productivity.

Considering these viewpoints together, the content of the internalolefin sulfonate in which a sulfonate group is present at a C-2 positionin the component (A) and the component (B) is, in the total content ofthe component (A) and the component (B), preferably 5% by mass or moreand 28% by mass or less, more preferably 7% by mass or more and lessthan 28% by mass, more preferably 7% by mass or more and less than 25%by mass, more preferably 15% by mass or more and 23% by mass or less,and even more preferably 19% by mass or more and 22% by mass or less.

A content of the a-olefin sulfonate in which the sulfonate group ispositioned at the C-1 position of an olefin chain or an alkane chain is,in the total content of the component (A) and the component (B),preferably less than 2.8% by mass and more preferably 2.0% by mass orless, from the viewpoint of light foam quality, and instantaneous foamdissipation property. The content of the α-olefin sulfonate in which thesulfonate group is positioned at the C-1 position of an olefin chain oran alkane chain is, in the total content of the component (A) and thecomponent (B), preferably 0.01% by mass or more, more preferably 0.1% bymass or more, and even more preferably 0.3% by mass or more, from theviewpoint of cost and productivity. Considering these viewpointstogether, the content of the α-olefin sulfonate in which the sulfonategroup is positioned at the C-1 position of an olefin chain or an alkanechain is, in the total content of the component (A) and the component(B), preferably 0.01% by mass or more and less than 2.8% by mass, morepreferably 0.1% by mass or more and less than 2.8% by mass, and evenmore preferably 0.3% by mass or more and less than 2.8% by mass.

It should be noted that the content of the internal olefin sulfonate inwhich the sulfonate group is present at the C-2 position in the internalolefin sulfonate having 12 and 14 carbon atoms may be measured by amethod such as nuclear magnetic resonance spectroscopy. Morespecifically, it is a numerical value measured by a method using gaschromatography described later in Example.

A content mass ratio of the hydroxy form to the olefin form, (hydroxyform/olefin form), in the internal olefin sulfonate having 12 and 14carbon atoms is preferably from 50/50 to 100/0, more preferably from60/40 to 100/0, more preferably from 70/30 to 100/0, more preferablyfrom 75/25 to 100/0, and even more preferably from 75/25 to 95/5, fromthe viewpoint of light foam quality, instantaneous foam dissipationproperty, and a feel after drying.

The content mass ratio of the hydroxy form and the olefin form in theinternal olefin sulfonate having 12 and 14 carbon atoms of the presentinvention may be measured by the method described later in Examples.

A content of an internal olefin sulfonate having 18 or more carbon atomsin the internal olefin sulfonate composition of the present invention ispreferably 5% by mass or less, more preferably 3% by mass or less, stillmore preferably 2% by mass or less, and even more preferably 1% by massor less, from the viewpoint of light foam quality, instantaneous foamdissipation property, and a feel after drying. The lower limit of thecontent of the internal olefin sulfonate having 18 or more carbon atomsis preferably 0% by mass, that is, it is preferable that the internalolefin sulfonate composition of the present invention does not containthe internal olefin sulfonate having 18 or more carbon atoms unless thisinternal olefin sulfonate is inevitably mixed therein.

For the internal olefin sulfonate having 18 or more carbon atoms, it isalso preferable to have a low content of the internal olefin sulfonatein which the sulfonate group is positioned at the C-2 position of anolefin chain or an alkane chain and a high content of the internalolefin sulfonate in which the sulfonate group is positioned moreinternally, from the viewpoint of light foam quality, instantaneous foamdissipation property, and a feel after drying.

As the internal olefin sulfonate composition of the present invention isobtained by sulfonating an internal olefin, followed by neutralizationand hydrolysis as described above, an unreacted raw material internalolefin and inorganic compounds may remain in the composition. It ispreferred that the contents of these components are much smaller.

A content of the raw material internal olefin in the internal olefinsulfonate composition of the present invention is preferably less than5.0% by mass, more preferably less than 3.0% by mass, more preferablyless than 1.5% by mass, more preferably less than 1.0% by mass and evenmore preferably less than 0.05% by mass with respect to the amount ofthe internal olefin sulfonates from the viewpoint of light foam quality,instantaneous foam dissipation property, and a feel after drying.

The content of the unreacted internal olefin may be measured by a methoddescribed later in Examples.

A content of inorganic compounds in the internal olefin sulfonatecomposition of the present invention is preferably less than 7.5% bymass, more preferably less than 5.0% by mass, more preferably less than3.0% by mass, and even more preferably less than 1.0% by mass withrespect to the amount of the internal olefin sulfonates from theviewpoint of light foam quality, instantaneous foam dissipationproperty, and a feel after drying.

In this context, the inorganic compound includes sulfate and alkaliagent. The content of these inorganic compounds may be measured by apotentiometric titration. Specifically, the content may be measured by amethod described later in Examples.

The internal olefin sulfonate composition of the present invention maycontain a hydroxy form and an olefin form having any number of carbonatoms which are different from that of the component (A) and thecomponent (B). The number of carbon atoms in the hydroxy form and theolefin form other than the component (A) and the component (B) ispreferably from 8 to 24, more preferably from 16 to 20, more preferablyfrom 16 to 18, and even more preferably 16 from the viewpoint of lightfoam quality, instantaneous foam dissipation property, and a feel afterdrying. These hydroxy forms and olefin forms having various numbers ofcarbon atoms are derived from the internal olefin used as a rawmaterial.

The internal olefin sulfonate composition of the present invention maycontain other components, for example, water as a medium, a pH adjuster,a viscosity reducing agent, an organic solvent, and polyhydric alcohols,in addition to the components described above.

<Method for Producing Internal Olefin Sulfonate Composition>

The internal olefin sulfonate composition may be produced by sulfonatinga raw material internal olefin composition containing a raw materialinternal olefin having 8 to 24 carbon atoms, followed by neutralizationand hydrolysis. More specifically, for example, the composition may beproduced in accordance with the methods described in U.S. Pat. Nos.1,633,184 and 2,625,150, and Tenside Surf. Det. 31 (5) 299 (1994), andthe like.

As mentioned above, in the present invention, a raw material internalolefin refers to an olefin substantially having a double bond inside theolefin chain. A content of the α-olefin in which a double bond ispresent at a C-1 position in the raw material internal olefin is, in thetotal content of the component (A) and the component (B), preferablyless than 2.8% by mass and more preferably 2.0% by mass or less, fromthe viewpoint of light foam quality, instantaneous foam dissipationproperty, and a feel after drying. The content of the α-olefin in whicha double bond is present at a C-1 position in the raw material internalolefin is, in the total content of the component (A) and the component(B), preferably 0.01% by mass or more, more preferably 0.1% by mass ormore, and even more preferably 0.3% by mass or more, from the viewpointof cost and productivity. Considering these viewpoints together, thecontent of the α-olefin sulfonate in which the sulfonate group ispositioned at the C-1 position of an olefin chain or an alkane chain is,in the total content of the component (A) and the component (B),preferably 0.01% by mass or more and less than 2.8% by mass, morepreferably 0.1% by mass or more and less than 2.8% by mass, morepreferably 0.3% by mass or more and less than 2.8% by mass, even morepreferably 0.3% by mass or more and 2.0% by mass or less.

From the viewpoint of light foam quality, instantaneous foam dissipationproperty of the internal olefin sulfonate composition obtained thus, thenumber of carbon atoms in the raw material internal olefin is preferablyfrom 8 to 24, more preferably from 12 to 20, more preferably from 12 to18, more preferably from 12 to 16, more preferably from 12 to 14, andeven more preferably 12 and 14. An internal olefin to be used as a rawmaterial may be used singly, or a combination of two or more thereof maybe used.

When the internal olefin sulfonate composition is obtained bysulfonating the raw material internal olefin composition, followed byneutralization and hydrolysis, the content of the internal olefin inwhich a double bond is present at a C-2 position in the raw materialinternal olefin composition is preferably from 15 to 40% by mass, andmore preferably from 15 to 35% by mass.

In the synthesis of the internal olefin sulfonate composition, thecontent of the raw material internal olefin in which a double bond ispresent at a C-2 position in the raw material internal olefincomposition may be measured by a gas chromatograph (hereinbelow,abbreviated as GC). Specifically, this content may be measured by themethod described later in Examples.

The raw material internal olefin composition may contain a paraffincomponent. A content of the paraffin component is preferably less than5% by mass, more preferably less than 3% by mass, more preferably 1% bymass or less, and even more preferably 0.1% by mass or less, from theviewpoint of foamability.

The content of the paraffin component may be measured, for example, byGC-MS.

The sulfonation reaction may be carried out by reacting a sulfurtrioxide gas with a raw material internal olefin composition at a ratioof from 1 to 1.2 moles of sulfur trioxide per mole of the raw materialinternal olefin. The reactions may be carried out at a reactiontemperature of from 20 to 40° C.

Neutralization is carried out by reacting from 1 to 1.5 times the molaramount of an alkaline aqueous solution such as sodium hydroxide,potassium hydroxide, ammonia or 2-aminoethanol with the theoreticalvalue of sulfonate group.

The hydrolysis reaction may be carried out at from 90 to 200° C. forfrom 30 minutes to three hours in the presence of water. These reactionsmay be successively carried out. Also, upon completion of the reactions,the products may be purified by extraction, washing, or the like.

In the production of the internal olefin sulfonate composition, the rawmaterial internal olefin in which the number of carbon atoms isdistributed in from 8 to 24 may be subjected as a raw material internalolefin composition to sulfonation, neutralization, and hydrolysis toproduce the internal olefin sulfonate composition. Alternatively, theraw material internal olefin having a uniform number of carbon atoms maybe subjected to sulfonation, neutralization, and hydrolysis to produceinternal olefin sulfonic acid, which is then mixed with a plurality ofinternal olefin sulfonates each having different number of carbon atomsto produce the internal olefin sulfonate composition.

The internal olefin sulfonate composition of the present inventionexerts good foamability together with light foam quality, andinstantaneous foam dissipation property at high levels, and is thususeful as a cleansing ingredient. Specifically, it can be used inhousehold cleansing agents such as hair shampoos, body cleansers,laundry detergents, and kitchen detergents, and is particularly usefulas a base for the hair shampoo.

<Cleansing Composition>

The cleansing composition of the present invention is not particularlylimited as long as it contains (A) an internal olefin sulfonate having12 carbon atoms and (B) an internal olefin sulfonate having 14 carbonatoms, wherein the content mass ratio of the component (A) to thecomponent (B), (A/B), is from 10/90 to 90/10, and the total content ofthe component (A) and the component (B) in the internal olefin sulfonateis from 60 to 100% by mass, as in the internal olefin sulfonatecomposition of the present invention. The cleansing composition of thepresent invention may contain other components depending on the intendedpurpose. Examples of the other components include other surfactant, afoaming increasing agent, and an auxiliary agent or the like. The totalcontent of the internal olefin sulfonate in the cleansing composition ispreferably from 0.1 to 80% by mass, more preferably from 1 to 50% bymass, and even more preferably from 2 to 30% by mass.

The other surfactant is preferably, for example, an alkyl sulfate or analkyl polyoxyalkylene sulfate. Examples of the auxiliary agent include,but not particularly limited to, water, polymer, an oil solution,silicone, a moisturizing agent, a viscosity regulator, a preservative,an anti-inflammatory agent, an antioxidant, an ultraviolet absorber, asequestering agent, a pearlescent agent, a dye, a fragrance, an enzyme,a bleaching agent, a bleach activator, and a pH adjuster.

The cleansing composition of the present invention may be produced, forexample, by formulating the internal olefin sulfonate compositionobtained as described above, and may be produced by further mixing theinternal olefin sulfonate composition with the components describedabove.

In relation to the embodiments mentioned above, the present inventionfurther discloses the following internal olefin sulfonate compositionand cleansing composition:

-   <1> An internal olefin sulfonate composition comprising (A) an    internal olefin sulfonate having 12 carbon atoms and (B) an internal    olefin sulfonate having 14 carbon atoms, wherein a content mass    ratio of the component (A) to the component (B), (A/B), is from    10/90 to 90/10, and a total content of the component (A) and the    component (B) is from 60 to 100% by mass.-   <2> The internal olefin sulfonate composition according to <1>,    wherein the content mass ratio of the component (A) to the component    (B), (A/B), in the internal olefin sulfonate composition is    preferably from 25/75 to 90/10, more preferably from 50/50 to 90/10,    more preferably from 75/25 to 90/10, and even more preferably from    80/20 to 90/10.-   <3> The internal olefin sulfonate composition according to <1>,    wherein the content mass ratio of the component (A) to the component    (B), (A/B), in the internal olefin sulfonate composition is    preferably from 10/90 to 80/20, more preferably from 10/90 to 70/30,    more preferably 10/90 to 30/70, and even more preferably from 10/90    to 20/80.-   <4> The internal olefin sulfonate composition according to any one    of <1> to <3>, wherein a lower limit of a total content of the    component (A) and the component (B) in the internal olefin sulfonate    composition is preferably 70% by mass or more, more preferably 80%    by mass or more, more preferably 90% by mass or more, more    preferably 95% by mass or more, more preferably 96.5% by mass or    more, and even more preferably 97% by mass or more.-   <5> The internal olefin sulfonate composition according to any one    of <1> to <4>, wherein a content of the internal olefin sulfonate in    which a sulfonate group is present at a C-2 position in the internal    olefin sulfonate having 12 and 14 carbon atoms is preferably 28% by    mass or less, more preferably less than 25% by mass, more preferably    23% by mass or less, and even more preferably 22% by mass or less,    and preferably 5% by mass or more, more preferably 7% by mass or    more, more preferably 15% by mass or more, and even more preferably    19% by mass or more.-   <6> The internal olefin sulfonate composition according to any one    of <1> to <5>, wherein a mass ratio of a content of a hydroxy form    to a content of an olefin form, (hydroxy form/olefin form), in the    internal olefin sulfonate having 12 and 14 carbon atoms is    preferably from 50/50 to 100/0, more preferably from 60/40 to 100/0,    more preferably from 70/30 to 100/0, more preferably from 75/25 to    100/0, and even more preferably from 75/25 to 95/5.-   <7> The internal olefin sulfonate composition according to any one    of <1> to <6>, wherein a content of an internal olefin sulfonate    having 18 or more carbon atoms is preferably 3% by mass or less,    more preferably 2% by mass or less, and even more preferably 1% by    mass or less, with its lower limit being preferably 0% by mass.-   <8> The internal olefin sulfonate composition according to any one    of <1> to <7>, wherein a content of a raw material internal olefin    in the internal olefin sulfonate composition is preferably less than    5.0% by mass, more preferably less than 3.0% by mass, more    preferably less than 1.5% by mass, more preferably less than 1.0% by    mass, and even more preferably less than 0.05% by mass with respect    to the amount of the internal olefin sulfonate.-   <9> The internal olefin sulfonate composition according to any one    of <1> to <8>, wherein a content of inorganic compound in the    internal olefin sulfonate composition is preferably less than 7.5%    by mass, more preferably less than 5.0% by mass, more preferably    less than 3.0% by mass, and even more preferably less than 1.0% by    mass with respect to the amount of the internal olefin sulfonates.-   <10> The internal olefin sulfonate composition according to any one    of <1> to <9>, wherein the number of carbon atom in the hydroxy form    and the olefin form other than the component (A) and the    component (B) in the internal olefin sulfonate composition is    preferably from 8 to 24, more preferably from 16 to 20, more    preferably from 16 to 18, and even more preferably 16.-   <11> The internal olefin sulfonate composition according to any one    of <1> to <10>, obtained by sulfonating a raw material internal    olefin composition containing a raw material internal olefin,    followed by neutralization and then hydrolysis, with a content of    the raw material internal olefin in which a double bond is present    at a C-2 position being preferably from 15 to 40% by mass.-   <12> The internal olefin sulfonate composition according to <11>,    wherein a content of the raw material internal olefin in which a    double bond is present at a C-2 position in the raw material    internal olefin composition is preferably from 15 to 35% by mass.-   <13> A cleansing composition obtained by formulating the internal    olefin sulfonate composition according to any one of <1> to <12>.-   <14> A cleansing composition comprising (A) an internal olefin    sulfonate having 12 carbon atoms and (B) an internal olefin    sulfonate having 14 carbon atoms, wherein a content mass ratio of    the component (A) to the component (B), (A/B), is from 10/90 to    90/10, and a total content of the component (A) and the    component (B) is from 60 to 100% by mass.-   <15> The cleansing composition according to <13> or <14>, wherein a    content of the internal olefin sulfonate is preferably from 0.1 to    80% by mass.-   <16> The cleansing composition according to any one of <13> to <15>,    further comprising one or more preferably selected from the group    consisting of an alkyl sulfate and an alkyl polyoxyalkylene sulfate.-   <17> A method for washing hair, comprising applying the cleansing    composition according to any one of <13> to <16> to hair, followed    by washing and then rinsing.-   <18> A method for washing skin, comprising applying the cleansing    composition according to any one of <13> to <16> to skin, followed    by rinsing.-   <19> Use of the cleansing composition according to any one of <13>    to <16> for washing hair.-   <20> Use of the cleansing composition according to any one of <13>    to <16> for washing skin.

EXAMPLES

Hereinbelow, the present invention will be specifically described withreference to Examples. It should be noted that unless otherwisespecifically noted, the content of each of the components is expressedby % by mass in the following Tables. Also, the methods for measuringvarious physical properties are as follows.

(1) Conditions of Measurement (i) Method for Measuring the Position of aDouble Bond in the Internal Olefin

The position of a double bond in an internal olefin was measured by gaschromatography (hereinbelow, abbreviated as GC). Specifically, aninternal olefin was converted to a dithiated derivative by reaction withdimethyl disulfide, and then each component was separated by GC. Theposition of a double bond in an internal olefin was determined by thepeak area of each component.

The apparatus and analytical conditions used for the measurement are asfollows. GC apparatus “HP6890” (the product of Hewlett-Packard Company);Column “Ultra-Alloy-1HT capillary column” (30 m×250 μm×0.15 μm, theproduct of Frontier Laboratories Ltd.); Detector (hydrogen flameionization detector (FID)); Injection temperature of 300° C.; Detectortemperature of 350° C.; and He flow rate of 4.6 mL/min.

(ii) Method for Measuring the Content of Internal Olefin Sulfonate inWhich a Sulfonate Group is Present at a C-2 Position

The linkage position of the sulfonate group was measured by GC.Specifically, the internal olefin sulfonate was reacted withtrimethylsilyldiazomethane to form a methyl-esterified derivative. Then,each component was separated by GC. Each of a peak area was regarded asa mass ratio, and the content of internal olefin sulfonate in which asulfonate group is present at a C-2 position was quantitated.

The apparatus and analytical conditions used for the measurement are asfollows. GC apparatus “Agilent technology 6850” (the product of AgilentTechnologies, Inc.); Column “HP-1 capillary column” (30 m×320 μm×0.25μm, the product of Agilent Technologies, Inc.); Detector (hydrogen flameionization detector (FID)); Injection temperature of 300° C.; Detectortemperature of 300° C.; He flow rate of 1.0 mL/min.; and Oven (60° C. (0min.)→10° C./min.→300° C. (10 min.)).

(iii) Method for Measuring the Mass Ratio of Hydroxy Form/Olefin Form

The mass ratio of hydroxy form/olefin form was measured by HPLC-MS.Specifically, the hydroxy form and the olefin form were separated byHPLC and each form was identified by separately analyzing with MS. Fromthe resulting GC-MS peak area, the fraction of each form was determined.

The apparatus and analytical conditions used for the measurement are asfollows. HPLC apparatus “Agilent technology 1100” (the product ofAgilent Technologies, Inc.); Column “L-column ODS 4.6×150 mm” (theproduct of Chemicals Evaluation and Research Institute, Japan); Samplepreparation (diluted 1000-fold with methanol); Eluent A (10 mM ammoniumacetate in water); Eluent B (10 mM ammonium acetate in methanol),Gradient (0 min (A/B=30/70%)→10 min (30/70%)→55 min (0/100%)→65 min(0/100%)→66 min (30/70%)→75 min (30/70%)); MS apparatus “Agilenttechnology 1100 MS SL (G1946D)” (the product of Agilent Technologies,Inc.); and MS detection (anion detection m/z 60-1600, UV 240 nm).

(iv) Method for Measuring the Content of the Raw Material InternalOlefin

The content of the raw material internal olefin was measured by GC.Specifically, ethanol and petroleum ether were added to an aqueoussolution of internal olefin sulfonate, followed by extraction to giveolefin in the petroleum ether phase. From the GC peak area of theolefin, the amount thereof was quantitated.

The apparatus and analytical conditions used for the measurement are asfollows. GC apparatus “Agilent technology 6850” (the product of AgilentTechnologies, Inc.); Column “Ultra-Alloy-1HT capillary column, 15 m×250μm×0.15 μm” (the product of Frontier Laboratories, Ltd.); Detector(hydrogen flame ionization detector (FID)); Injection temperature of300° C.; Detector temperature of 350° C.; and He flow rate of 3.8mL/min.

(v) Method for Measuring the Content of Inorganic Compound

The content of inorganic compound was measured by potentiometrictitration and neutralization titration. Specifically, the content ofNa₂SO₄ was quantitated by measuring sulfate ion (SO₄ ²⁻) bypotentiometric titration. Also, the content of NaOH was quantitated byneutralization titration with diluted hydrochloric acid.

(vi) Method for Measuring the Content of the Paraffin Component

The content of the paraffin component was measured by GC. Specifically,ethanol and petroleum ether were added to an aqueous solution ofinternal olefin sulfonate, followed by extraction to give paraffin inthe petroleum ether phase. From the GC peak area of the paraffin, theamount thereof was quantitated.

It should be noted that the apparatus and analytical conditions used arethe same as those used for the measurement of the content of the rawmaterial internal olefin.

(2) Production of an Internal Olefin Production Example A Synthesis ofC12 Internal Olefin in which 33.1% by Mass of Double Bond was Present atC-2 Position

Into a flask with a stirrer, (6000 g (35.6 moles) of 1-dodecene“LINEALENE 12, manufactured by Idemitsu Kosan Co., Ltd.”, and as a solidacid catalyst, 180 g (3% by mass relative to the raw material a-olefin)of protic β-zeolite (CP-814E, Zeolyst International, Inc.) were placed,and the reaction was allowed to proceed for 20 hours at 120° C. whilestirring. Subsequently, the crude internal olefin was transferred to adistillation flask and distilled at from 124 to 136° C./7.5 mmHg,whereby 100% pure internal olefin having 12 carbon atoms was obtained.The double bond distribution in the resulting internal olefin was 0.5%by mass at C-1 position, 33.1% by mass at C-2 position, 23.7% by mass atC-3 position, 21.2% by mass at C-4 position, 15.0% by mass at C-5position, and 6.6% by mass at C-6 position.

Production Example B Synthesis of C14 Internal Olefin in which 31.8% byMass of Double Bond was Present at C-2 Position

Into a flask with a stirrer, 6000 g (30.6 moles) of 1-tetradecene“LINEALENE 14, manufactured by Idemitsu Kosan Co., Ltd. “, and as asolid acid catalyst, 180 g (3% by mass relative to the raw materialα-olefin) of protic β-zeolite (CP-814E, Zeolyst International, Inc.)were placed, and the reaction was allowed to proceed for 20 hours at120° C. while stirring. Subsequently, the crude internal olefin wastransferred to a distillation flask and distilled at from 124 to 136°C./7.5 mmHg, whereby 100% pure internal olefin having 14 carbon atomswas obtained. The double bond distribution in the resulting internalolefin was 1.3% by mass at C-1 position, 31.8% by mass at C-2 position,23.8% by mass at C-3 position, 21.0% by mass at C-4 position, 8.6% bymass at C-5 position, and 13.6% by mass at sum of C-6 and C-7 positions.

(3) Production of an Internal Olefin Sulfonate Production Example 1Synthesis of C12 Internal Olefin Sulfonate

Into a thin film sulfonation reactor having an outer jacket, theinternal olefin having 12 carbon atoms (the content of an internalolefin in which a double bond is present at a C-2 position is 33.1% bymass) obtained in Production Example A was placed, and the sulfonationreaction was carried out by using sulfur trioxide gas under conditionsof passing cooling water at 20° C. through the outer jacket of thereactor. The molar ratio of SO₃/internal olefin for the sulfonationreaction was set at 1.09. The resulting sulfonation product was added toan alkaline aqueous solution prepared with 1.5 times the molar amount ofsodium hydroxide relative to the theoretical acid value, followed byneutralization at 30° C. for one hour while stirring. The resultingneutralized product was hydrolyzed by heating at 160° C. for one hour inan autoclave, whereby a crude product of sodium C12 internal olefinsulfonate was obtained. Then, 300 g of the crude product was transferredto a separatory funnel, to which 300 mL of ethanol was added and then300 mL of petroleum ether was added per operation, whereby oil-solubleimpurities were removed by extraction. At this time, inorganic compounds(mainly composed of sodium sulfate) which were precipitated at theoil-water interface by the addition of ethanol were also separated andremoved from the aqueous phase by the oil-water separation operation.The above removal/extraction operation was repeated three times. Then,the aqueous phase side was evaporated to dryness, whereby sodium C12internal olefin sulfonate was obtained. The mass ratio of hydroxy form(sodium hydroxyalkane sulfonate)/olefin form (sodium olefin sulfonate)in the obtained sodium internal olefin sulfonate was 92/8. Also, thecontent of the raw material internal olefin contained in the obtainedsodium internal olefin sulfonate was less than 100 ppm (below the GCdetection limit), and that of inorganic compounds was 0.2% by mass.Also, the content of an internal olefin sulfonate in which a sulfonategroup is present at a C-2 position was 21.0% by mass.

Production Example 2 Synthesis of C14 Internal Olefin Sulfonate

A sodium C14 internal olefin sulfonate was obtained under the sameconditions as those used in Production Example 1 from the internalolefin having 14 carbon atoms (the content of an internal olefin inwhich a double bond is present at a C-2 position is 31.8% by mass)obtained in Production Example B.

The mass ratio of hydroxy form/olefin form in the obtained sodiuminternal olefin sulfonate was 93/7. Also, the content of the rawmaterial internal olefin contained in the obtained sodium internalolefin sulfonate was less than 100 ppm (below the GC detection limit)and that of inorganic compounds was 0% by mass. The content of aninternal olefin sulfonate in which a sulfonate group is present at C-2position was 21.7% by mass.

Production Example 3

The composition obtained in Production Example 1 and the compositionobtained in Production Example 2 were formulated and mixed at a massratio of 10:90 to obtain internal olefin sulfonate composition 1.

Production Example 4

The composition obtained in Production Example 1 and the compositionobtained in Production Example 2 were formulated and mixed at a massratio of 25:75 to obtain internal olefin sulfonate composition 2.

Production Example 5

The composition obtained in Production Example 1 and the compositionobtained in Production Example 2 were formulated and mixed at a massratio of 50:50 to obtain internal olefin sulfonate composition 3.

Production Example 6

The composition obtained in Production Example 1 and the compositionobtained in Production Example 2 were formulated and mixed at a massratio of 75:25 to obtain internal olefin sulfonate composition 4.

Production Example 7

The composition obtained in Production Example 1 and the compositionobtained in Production Example 2 were formulated and mixed at a massratio of 90:10 to obtain internal olefin sulfonate composition 5.

<Hair Evaluation>

A hair bundle (hair of a Japanese person free from treatment such asbleach or hair color; approximately 20 cm, 15 g) was cleansed with aplain shampoo shown in Table 1. Then, after application of a plain rinseshown in Table 2, the hair bundle was rinsed off with tap water toobtain a tress for evaluation.

Each of the internal olefin sulfonate compositions 1 to 5 obtained inProduction Examples 3 to 7 was dissolved in ion-exchange water toprepare an aqueous solution (13% by mass) of the internal olefinsulfonate composition. Using these aqueous solutions, five expertpanelists evaluated their foamability, light foam quality, foamdissipation property during rinsing, and feel after cleansing andsubsequent towel drying (without perceivable residues) in accordancewith evaluation criteria and evaluation methods shown below.(Specifically, 1.0 g of each cleansing composition shown in Table 3 wasapplied to the tress for evaluation and subjected to lathering,cleansing, and then rinsing.) The results are shown in Table 3.

Table 3 also shows the evaluation results with reference to alkylpolyoxyethylene sulfate (AES), α-olefin sulfonate (AOS), and secondaryalkyl sulfonate (SAS). The concentrations of these surfactants in thecleansing compositions were adjusted to 13% by mass.

TABLE 1 (Composition of plain shampoo) (Component) (%) Sodiumpolyoxyethylene lauryl ether sulfate 11.3 (42.0% in terms of EMAL E-27C(manufactured by Kao Corp.; 27% by weight of active component)) Coconutoil fatty acid N-methylethanolamide 3.0 (AMINON C-11S (manufactured byKao Corp.)) Citric acid 0.2 Methylparaben 0.3 Purified water BalanceTotal 100.0

(Production of Plain Shampoo)

The components were placed in a beaker, heated to 80° C., and thenmixed. After confirmation of uniform dissolution, the mixture was cooledto obtain a plain shampoo.

TABLE 2 (Composition of plain rinse) (Component) (%) Octadecyloxypropyltrimethyl ammonium chloride 3.0 (6.7% in terms of QUARTAMIN E-80K(manufactured by Kao Corp.; 45% by weight of active component)) Stearylalcohol 6.0 (KALCOL 8098 (manufactured by Kao Corp.)) Methylparaben 0.3Purified water Balance Total 100.0

(Production of Plain Rinse)

Octadecyloxypropyl trimethyl ammonium chloride and stearyl alcohol wereplaced in a beaker (A) and melted by heating to 80° C. Purified waterand methylparaben were placed in another beaker (B) and heated to 80° C.while stirring. After confirmation of uniform dissolution, the mixedsolution in the beaker (A) was added to the beaker (B) while stirring at80° C., and an emulsification was carried out for 30 minutes. Theheating was terminated, and it was cooled to room temperature to obtaina plain rinse.

<Evaluation Criteria and Evaluation Methods>

-   Foamability-   5: Foaming properties were very good-   4: Foaming properties were good-   3: Ordinary foamability (equivalent to Reference Comparative Example    3: SAS)-   2: Foaming properties were poor-   1: Foaming properties were too poor to cleanse hair

Light Foam Quality

-   5: Foam quality was very light and promoted cleansing with large    bubbles-   4: Foam quality was slightly light and good-   3: Foam quality was ordinary (equivalent to Reference Comparative    Example 1: AES)-   2: Foam quality was slightly heavy and poor-   1: Foam quality was very heavy and hindered cleansing

Foam Dissipation Property During Rinsing

-   5: Foam was dissipated in the moment of rinsing and easily rinsed-   4: Foam was quickly dissipated-   3: Ordinary (equivalent to Reference Comparative Example 2: AOS)-   2: Foam was slowly dissipated-   1: Foam was very slowly dissipated and was difficult to rinse

Feel After Cleansing and Subsequent Towel Drying

-   5: Cleansing finish was very refreshing without perceivable residues    from the cleansing agent-   4: Cleansing finish was slightly refreshing-   3: Ordinary (equivalent to Reference Comparative Example 1: AES)-   2: Cleansing finish was hardly refreshing with slightly perceivable    residues from the cleansing agent-   1: Cleansing finish was not refreshing with strongly perceivable    residues from the cleansing agent

<Hand Wash Evaluation>

Each of the internal olefin sulfonate compositions 1 to 5 obtained inProduction Examples 3 to 7 was dissolved in ion-exchange water toprepare an aqueous solution (13% by mass) of the internal olefinsulfonate composition. Using these aqueous solutions, five panelistswashed their hands, and evaluated foamability, foam dissipation propertyduring rinsing, and feel after cleansing and subsequent towel drying(without perceivable residues) in accordance with the followingevaluation criteria and evaluation method. Specifically, 1.0 g ofaqueous solution (13% by mass) prepared by using the internal olefinsulfonate compositions shown in Table 3 was applied to the hands andsubjected to lathering, cleansing, and then rinsing, and subsequenttowel drying. The results are shown in Table 3.

Foamability

-   5: Foaming properties were very good-   4: Foaming properties were good-   3: Ordinary foamability (equivalent to Reference Comparative Example    3: SAS)-   2: Foaming properties were poor-   1: Foaming properties were too poor to cleanse hand

Foam Dissipation Property During Rinsing

-   5: Foam was dissipated in the moment of rinsing and easily rinsed-   4: Foam was quickly dissipated-   3: Ordinary (equivalent to Reference Comparative Example 2: AOS)-   2: Foam was slowly dissipated-   1: Foam was very slowly dissipated and was difficult to rinse

Feel After Cleansing and Subsequent Towel Drying

-   5: Cleansing finish was very refreshing without perceivable residues    from the cleansing agent-   4: Cleansing finish was slightly refreshing-   3: Ordinary (equivalent to Reference Comparative Example 2: AOS)-   2: Cleansing finish was hardly refreshing with slightly perceivable    residues from the cleansing agent-   1: Cleansing finish was not refreshing with strongly perceivable    residues from the cleansing agent

TABLE 3 Reference Internal olefin sulfonate composition ComparativeExamples 1 2 3 4 5 1 2 3 Internal The number of carbon atoms in internalolefin 12/14 12/14 12/14 12/14 12/14 AES*1 AOS*2 SAS*3 olefin sulfonate(mass ratio within parentheses) (10/90) (25/75) (50/50) (75/25) (90/10)sulfonate Total content of C12/14 (%) 100 100 100 100 100 compositionAmount of raw material internal olefin relative <100 ppm <100 ppm <100ppm <100 ppm <100 ppm to amount of C12/14 internal olefin sulfonateHydroxy form/olefin form in C12/14 internal 93/7  93/7  92/8  92/8 92/8  olefin sulfonate Ratio of sulfonate group present at C-2 position21.6 21.5 21.4 21.2 21.1 in C12/14 internal olefin sulfonate (%) Ratioof double bond present at C-2 position in 31.9 32.1 32.4 32.7 32.9 rawmaterial internal olefin (%) Amount of inorganic compound (%) 0.0 0.10.1 0.2 0.2 Evaluation Hair Foamability 5.0 4.6 4.2 4.0 3.8 2.0 2.4 3.0results evaluation Foam quality (lightness) 4.2 4.4 4.6 4.8 5.0 3.0 3.63.4 Foam dissipation property 4.4 4.6 4.6 4.8 5.0 2.4 3.0 2.0 Feel afterdrying 4.2 4.4 4.6 5.0 5.0 3.0 3.4 2.4 (without perceivable residues)Hand wash Foamability 5.0 4.8 4.4 4.2 3.8 2.0 2.0 3.0 evaluation Foamdissipation property 4.6 4.8 4.8 5.0 5.0 2.0 3.0 1.4 Feel after drying4.2 4.4 4.6 4.8 5.0 2.6 3.0 1.8 (without perceivable residues) *1Sodiumalkyl polyoxyethylene sulfate (AES), manufactured by Kao Corp., EMAL270S (active component: 70%) *2Sodium α-olefin sulfonate (AOS),manufactured by Lion Corp., LIPOLAN LB-440 (active component: 36%)*3Secondary sodium alkyl sulfonate (SAS), manufactured by LANXESS K.K.,Mersolat H95 (active component: 95%)

INDUSTRIAL APPLICABILITY

The internal olefin sulfonate composition of the present invention canexert good foamability together with light foam quality, andinstantaneous foam dissipation property at high levels. Thus, theinternal olefin sulfonate composition of the present invention can beused suitably in the fields of household cleansing agents such as hairshampoos, body cleansers, laundry detergents, kitchen detergents, andresidential detergents, and is also suitable for cosmetic emulsifiers,industrial emulsifiers, industrial cleansing agents or the like.

1. An internal olefin sulfonate composition comprising (A) an internalolefin sulfonate having 12 carbon atoms and (B) an internal olefinsulfonate having 14 carbon atoms, wherein a content mass ratio of thecomponent (A) to the component (B), (A/B), is from 10/90 to 90/10. 2.The internal olefin sulfonate composition according to claim 1, whereina content of the internal olefin sulfonate in which a sulfonate group ispresent at a C-2 position in the internal olefin sulfonate having 12 and14 carbon atoms is 28% by mass or less.
 3. The internal olefin sulfonatecomposition according to claim 1, wherein a mass ratio of a content of ahydroxy form in the internal olefin sulfonate having 12 and 14 carbonatoms to a content of an olefin form in the internal olefin sulfonatehaving 12 and 14 carbon atoms, (hydroxy form/olefin form), is from 50/50to 100/0.
 4. The internal olefin sulfonate composition according toclaim 1, wherein a content of a raw material internal olefin in theinternal olefin sulfonate composition is less than 5.0% by mass withrespect to the amount of the internal olefin sulfonate.
 5. The internalolefin sulfonate composition according to claim 1, wherein a the contentof an inorganic compound in the internal olefin sulfonate composition isless than 7.5% by mass with respect to the amount of the internal olefinsulfonate.
 6. The internal olefin sulfonate composition according toclaim 1, obtained by sulfonating a raw material internal olefincomposition containing a raw material internal olefin, followed byneutralization and then hydrolysis, with a content of the raw materialinternal olefin in which a double bond is present at a C-2 positionbeing from 15 to 40% by mass.
 7. The internal olefin sulfonatecomposition according to claim 1, wherein a content mass ratio of thecomponent (A) to the component (B), (A/B), in the internal olefinsulfonate composition is from 75/25 to 90/10.
 8. The internal olefinsulfonate composition according to claim 1, wherein a content mass ratioof the component (A) to the component (B), (A/B), in the internal olefinsulfonate composition is from 10/90 to 30/70.
 9. A cleansing compositionobtained by formulating the internal olefin sulfonate compositionaccording to claim
 1. 10. A cleansing composition comprising (A) aninternal olefin sulfonate having 12 carbon atoms and (B) an internalolefin sulfonate having 14 carbon atoms, wherein a content mass ratio ofthe component (A) to the component (B), (A/B), is from 10/90 to 90/10.11. The cleansing composition according to claim 10, wherein a totalcontent of (A) the internal olefin sulfonate having 12 carbon atoms and(B) the internal olefin sulfonate having 14 carbon atoms is from 0.1 to80% by mass.
 12. The cleansing composition according to claim 10,comprising one or more selected from the group consisting of an alkylsulfate and an alkyl polyoxyalkylene sulfate.